Catalyst and process for selective production of lower hydrocarbons C1—C5 from syngas with low methane and CO2 production

ABSTRACT

A catalyst composition containing cobalt manganese oxide which is modified with silicon in the form of a hydrophilic silica, the catalyst also containing at least one of lanthanum, phosphorus, Fe, Zr, and Zn, and optionally one or more basic elements selected from the group of alkali metal, alkaline earth metal, and transition metals. Also, methods for preparing and using the catalyst composition for producing aliphatic and aromatic hydrocarbons using the catalyst composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of and claims the benefit ofpriority to U.S. Application No. 14/409,017, filed Dec. 18, 2014, whichis a U.S. National Phase Application of International Application No.PCT/EP2013/063311, filed Jun. 25, 2013, which claims priority to U.S.Application No. 61/665,005, filed Jun. 27, 2012, all of whichapplications are incorporated herein fully by this reference.

BACKGROUND

Gaseous mixtures comprising hydrogen (H₂) and carbon monoxide (CO) canbe converted into a hydrocarbon product stream by a catalytic processknown as Fischer-Tropsch synthesis (F-T synthesis). The most commoncatalysts useful in F-T synthesis (“F-T catalysts”) are based on Feand/or Co, although Ni- and Ru-based catalysts have also been described(see e.g. U.S. Pat. No. 4,177,203; Commereuc (1980) J. Chem. Soc., Chem.Commun. 154-155; Okuhara (1981) J. Chem. Soc., Chem. Commun. 1114-1115).Generally, Ni-based catalysts are relatively more selective forproducing methane whereas Co-, Fe- and Ru-based catalysts are moreselective for hydrocarbons having at least two carbon atoms (C₂₊hydrocarbons). Moreover, the selectivity for C₂₊ hydrocarbons can beincreased by decreasing the H₂:CO ratio, decreasing the reactiontemperature and decreasing the reactor pressure.

It has been previously described that unsupported cobalt-manganese oxidecatalysts can be used as an F-T catalyst having an improved selectivityfor C₃ hydrocarbons and a suppressed CH₄ selectivity (see Van der Riet(1986) J. Chem. Soc. Chem. Commun 798-799 and Keyser (1998) AppliedCatalysis 171:99-107). The unsupported cobalt-manganese oxidecomposition suitable for use as F-T catalyst was produced by a processcomprising the steps of co-precipitating cobalt and manganese oxidesfrom cobalt- and manganese-comprising solution, calcining theprecipitate to form a calcined catalyst precursor and reducing thecalcined catalyst precursor to obtain the cobalt-manganese oxidecatalyst composition (see Colley (1988) Ind. Eng. Chem. Res.27:1339-1344). It was found that the catalyst precursor comprised themixed spinels Co₂MnO₄ and Co₂Mn₂O₄. Reduction of the catalyst precursorresulted in an unsupported catalyst composition comprising metallic Co,MnO and a certain amount of mixed spinels Co₂MnO₄ and Co₂Mn₂O₄.

It was the disadvantage of the prior art that F-T synthesis ofhydrocarbon products result in a mixture of undesired products and lessdesired olefin products. A major drawback of conventional unsupportedcobalt-manganese oxide F-T catalysts is their relatively low activityresulting in a relatively low syngas conversion rate.

It was an object of the present invention to provide an improvedFischer-Tropsch catalyst (F-T catalyst) having superior catalystactivity while maintaining high hydrocarbon selectivity and low carbondioxide (CO₂) and methane (CH₄) selectivity. In another aspect, it wasan object of the present invention to provide an improved process forproducing a higher yield of ethylene and propylene from syngas inaddition to value added products, such as 1-hexene and 1-butene.

SUMMARY

The present invention relates to a catalyst composition comprisingcobalt manganese oxide which is modified with silica in the form of ahydrophilic silica, the catalyst further comprises at least one oflanthanum, phosphorus, Fe, Zr and Zn and optionally one or more basicelements selected from the group consisting of alkali metal, alkalineearth metal and transition metal. Furthermore, a method for preparingsaid catalyst composition and a process for producing aliphatic andaromatic hydrocarbons using said catalyst composition is provided.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows a scheme of an embodiment of the process according to thepresent invention.

FIG. 2 shows a further embodiment of the process according to thepresent invention.

DETAILED DESCRIPTION

Compositions

The solution to the above problem is achieved by providing theembodiments as described herein below and as characterized in theclaims. Accordingly, the present invention provides a catalystcomposition comprising cobalt; manganese; a hydrophilic silica; and atleast one element selected from the group of lanthanum, phosphorus, Fe,Zr and Zn, wherein the relative molar ratios of the elements comprisedin said composition are represented by the formulaCoMn_(a)Si_(b)X_(c)M_(d)O_(y)

-   -   wherein:        -   M is one or more elements selected from the group consisting            of alkali metal, alkaline earth metal and transition metal;        -   a is from about 0.8 to about 1.2;        -   b is from about 0.1 to about 1;        -   each c is from greater than 0 to about 0.005, wherein the            total c is from greater than 0 to about 0.005;        -   d is from about 0 to about 0.005;        -   X is at least one element selected from the group consisting            of lanthanum, phosphorus, Fe, Zr and Zn;        -   y is a number determined by the valence of the other            elements present; and        -   Si is in the form of a hydrophilic silica.

In the context of the present invention, it was surprisingly found thatthe catalyst activity of a conventional cobalt manganese oxideFT-catalyst can be significantly increased when said conventionalcatalyst is modified with a hydrophilic silica, such as, for example, anAEROSIL® hydrophilic silica from Evonik, and at least one elementselected from the group consisting of lanthanum, phosphorus, Fe, Zr andZn and optionally one or more elements selected from the groupconsisting of alkali metal, alkaline earth metal and transition metal.Furthermore, it was found that the catalyst of the present invention hasa decreased selectivity for CO₂ and CH₄ which are unwanted side productsof F-T synthesis. Hence, the catalyst provided by the present inventionis particularly suitable for converting a syngas mixture into ahydrocarbon comprising product stream. In one aspect, the hydrocarbon isan olefin.

The molar ratio of Co:Mn is about 1:0.8-1.2 (depicted as: CoMn_(a)wherein a is 0.8-1.2). This means that the molar ratio of Co:Mn isbetween about 1:0.8: and about 1:1.2. In another aspect, the molar ratioof Co:Mn is about 1:0.9-1.1. In yet another aspect, the molar ratio ofCo:Mn is about 1:1. The molar ratio of Co:Mn can be important to obtaina catalyst composition having a high light olefin selectivity and a lowmethane selectivity. The relative ratio of cobalt and manganese has astrong effect on selectivity of the catalyst for hydrocarbons. When theCo:Mo ratio is too high, the hydrogenation activity of the catalyst isincreased leading to an increased methane selectivity.

The catalyst composition of the present invention comprises silicon inthe form of a hydrophilic silica (depicted as: Si_(b) wherein b is 0.1to 1). The subscript ‘b’ is intended to refer to the molar ratio of theSi relative to Co. Thus, for example, Co:Si_(b) is 1:0.1 to 1. In oneaspect, Si_(b) is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1.0. Inone aspect, the hydrophilic silica can have a pH of from about 3.7 toabout 4.7, for example, about 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5,4.6, or 4.7. In another aspect, the hydrophilic silica can have a pHless than about 3.7 or greater than about 4.7 and the present inventionis not intended to be limited to a hydrophilic silica having anyparticular pH value. In another aspect, the hydrophilic silica has aspecific surface area of from about 200 m²/g to about 400 m²/g, forexample, about 200, 225, 250, 275, 300, 325, 350, 375, or 400 m²/g.Similarly, in other aspects, the hydrophilic silica can have a specificsurface area less than about 200 m²/g or greater than about 400 m²/g andthe present invention is not intended to be limited to a hydrophilicsilica having any particular specific surface area. In one aspect, thehydrophilic silica is a pyrogenic silica, having a low bulk density andproduced from a flame based process. In another aspect, the hydrophilicsilica can comprise an AEROSIL® silica, available from EvonikIndustries.

The catalyst composition of the present invention also comprises atleast one element selected from the group consisting of lanthanum,phosphorus, Fe, Zr and Zn (depicted as X_(c) wherein each c is fromgreater than 0 to about 0.005, wherein the total c is from greater than0 to about 0.005). In one aspect, the catalyst composition comprises oneelement. If the catalyst composition comprises one element, the elementcan be selected from the group consisting of Fe, Zr, and Zn. In anotheraspect, the catalyst composition comprises two elements. If the catalystcomposition comprises two elements, the elements can be lanthanum andphosphorus. In one embodiment, accordingly, the catalyst compriseslanthanum but does not comprise phosphorus. In one embodiment, thecatalyst comprises phosphorus but does not comprise lanthanum. In yetanother embodiment, the catalyst comprises both lanthanum andphosphorus. For example, if the catalyst composition comprises bothlanthanum and phosphorus, then c for each lanthanum and phosphorus isfrom greater than 0 to about 0.005, wherein the total c is from greaterthan 0 to about 0.005. Thus, when X is more than one element, forexample two elements, the value of c for the first element added to thevalue of c for the second element has a value of from greater than 0 toabout 0.005. In one aspect, the molar ratio of Co:X is at least 1: about10⁻⁶ in case the catalyst composition comprises lanthanum; at least 1:about 10⁻⁵; or at least 1: about 5×10⁻⁵. In one aspect, the molar ratioof Co:P is at least 1: about 10⁻⁶ in case the catalyst compositioncomprises phosphorus; at least 1: about 10⁻⁵; or at least 1: about5×10⁻⁵. c refers to the molar ratio of the Si relative to X. Thus, forexample, Co:X_(c) is greater than 0 to about 0.005. The term “greaterthan 0” means that said element can be present in the catalystcomposition.

The catalyst composition of the present invention further can compriseone or more additional elements selected from the group consisting ofalkali metal element, alkaline earth metal element and transition metalelement (depicted herein as “M”). In the context of the presentinvention, it was found that CO₂ formation and the therewith associatedcoke deposition by the Boudouard reaction can be suppressed when thecatalyst composition further comprises one or more basic elementsselected from the group consisting of alkali metal elements, alkalineearth metal elements and transition metal elements. As used herein, theterm “basic element” relates to an element that forms a “Lewis base”(i.e. an element that is able to provide a pair of electrons and thuscapable of coordination to a Lewis acid, thereby producing a Lewisadduct) and/or a “Brønsted base” (i.e. an element capable of accepting aproton from a acid or the corresponding chemical species) in thecatalyst composition.

In one aspect, the one or more alkali metals that can be in the catalystcomposition are selected from the group consisting of sodium (Na),potassium (K), rubidium (Rb) and caesium (Cs). In another aspect, theone or more alkali metals are selected from the group consisting ofsodium (Na), potassium (K) and caesium (Cs). In yet another aspect, theone or more alkali metals is potassium (K). The one or more alkalineearth metals that can be in the catalyst composition can be selectedfrom the group consisting of magnesium (Mg), calcium (Ca), strontium(Sr) and barium (Ba); or selected from the group consisting of magnesium(Mg) and calcium (Ca). The one or more transition metal elements thatcan be in the catalyst composition of the present invention can beselected from “Group 4 of the Periodic Table” or from the groupconsisting of titanium (Ti) and zirconium (Zr).

The amount of alkali metal, alkaline earth metal and/or transition metalelements (“M”) that can be in the catalyst composition of the presentinvention is determined by the molar ratio in relation to the cobaltpresent in the catalyst composition. In case the catalyst compositioncomprises M, the molar ratio Co:M is up to 1: about 0.005 (1: about5×10⁻³; also depicted as: CoM_(d) wherein d is from greater than 0 toabout 0.005), or up to 1: about 10⁻³. In another aspect, the molar ratioof Co:M is at least 1: about 10⁻⁶ in case the catalyst compositioncomprises M; at least 1: about 10⁻⁵; or at least 1: about 5×10⁻⁵. d canalso be 0, meaning that M is absent.

In this respect, it should be noted that the catalyst of the presentinvention is a mixed oxide catalyst and not a catalyst wherein theactive elements are deposited on a catalyst support. The unsupportedcatalyst of the present invention is fundamentally different than F-Tcatalysts wherein Co and Mn are deposited on a (metal) oxide catalystsupport. Nevertheless, the catalyst composition can further comprise a(metal) oxide, e.g. as a binder or a diluent.

Accordingly, the catalyst composition of the present invention canfurther comprise a binder (support or substrate) which can be selectedfrom the group consisting of magnesia, alumina, silica, zirconia,titania, activated carbon, non-activated carbon, or zeolites. Thezeolite, if present, can be a mesoporous zeolite or a microporouszeolite. In one aspect, the binder can be fluidized. In another aspect,the binder can be a shaped form.

The catalyst composition can have at least a lower methane formation, alower carbon dioxide formation, a higher activity, a higher activity, ahigher conversion of syngas, or a higher total olefins formation ascompared to a the same catalyst without the Si_(b) component. Thus, forexample, a catalyst composition comprising Si_(b), lanthanum andphosphorus can have a higher total olefin formation than a catalystcomposition without the Si_(b) component but with the lanthanum andphosphorus. In another example, a catalyst composition comprisingSi_(b), lanthanum and phosphorus can covert more CO in syngas that acatalyst composition without the Si_(b) component but with the lanthanumand phosphorus.

Methods

Also disclosed herein, is a method of producing olefins comprisingcontacting syngas with the catalyst compositions described herein.

Also disclosed herein, is a method of making a catalyst composition asdescribed herein.

In a further embodiment, the present invention relates to a method forpreparing the catalyst composition as described herein, wherein saidmethod comprises the steps:

-   (a) preparing a solution of cobalt- and manganese-comprising salts    to form a cobalt-manganese-solution;-   (b) admixing an alkaline solution to the cobalt-manganese-solution    to form a precipitate;-   (c) admixing a hydrophilic silica and a solution of at least one    lanthanum, phosphorus, Fe, Zr and Zn salt; such as, for example, a    solution of a salt comprising one or more elements selected from the    group consisting of alkali metal elements, alkaline earth metal    elements and transition metal elements to the solution comprising    the precipitate of Co and Mn formed in step (b to form a modified    precipitate;-   (d) separating the modified precipitate from the liquid, washing and    drying the modified precipitate to form a dried precipitate;-   (e) calcining the dried precipitate in air to form a calcined    catalyst precursor; and-   (f) contacting the calcined catalyst precursor with a reducing    agent.

Suitable reducing agents include, but are not limited to, CO and H₂.

In another aspect, the method for preparing the catalyst composition ofthe invention comprises the steps (a)-(f) in the herein above describedorder.

In the cobalt-manganese-solution preparation step (a) as describedherein, a solution comprising soluble cobalt- and manganese-comprisingsalts is prepared. The solvent and the obtained solution can be heatedto facilitate dissolving of the cobalt- and manganese-comprising salts.In another aspect, the solvent and the obtained solution is heated to atleast about 60° C. and up to about 95° C. (about 60-95° C.), or to about80° C.

In the present method for preparing the catalyst composition, thesolution can be made in any suitable solvent. Suitable solvents are allcompounds in which the chosen salts are soluble and which are easy toremove again in the separation step as defined herein. In one aspect, anaqueous solution can be used. In a specific aspect, the solvent is water(H₂O).

In the precipitate forming step (b) as described herein, a precipitateis formed by converting the soluble cobalt- and manganese-comprisingsalts into insoluble compounds by admixing an alkaline solution, forexample, under constant agitation. In one aspect, the precipitate isformed by admixing a suitable amount of ammonium hydroxide and/or sodiumcarbonate solution, such as, for example, ammonium hydroxide solution,to a cobalt-manganese-solution. The amount of alkaline compound presentin the alkaline solution is selected so that it is at least sufficientfor the stoichiometric reaction with the soluble cobalt- andmanganese-comprising salts present. In another aspect, the amount ofalkaline compound present in the alkaline solution is 1-10 times thestoichiometric amount. In yet another aspect, the ammonium hydroxideand/or sodium carbonate solution is heated to the same temperature asthe cobalt-manganese-solution. The temperature of the mixture can bekept constant until the precipitate is formed under constant agitation.

In the modified precipitate forming step (c) as described herein, asolution of a hydrophilic silica is admixed with a solution containingat least one of a lanthanum, phosphorus, Fe, Zr, and Zn salt, such as alanthanum-comprising salt; and/or a solution of a phosphorus-comprisingsalt; such as, for example, a solution of a salt comprising one or moreelements selected from the group consisting of the alkali metalelements, the alkaline earth metal elements and the transition metalelements is admixed to the solution comprising the Co/Mn precipitateformed in step (b) of the method, for example, under continuousagitation, to form a modified precipitate. The solution of a saltcomprising one or more elements selected from the group consisting ofthe alkali metal elements, the alkaline earth metal elements and thetransition metal elements can be added at the same time or after addingthe solution of a lanthanum-comprising salt; and/or a solution of aphosphorus-comprising salt. In another aspect, the solution of a saltcomprising one or more elements selected from the group consisting ofthe alkali metal elements, the alkaline earth metal elements and thetransition metal elements is added after adding the solution of alanthanum-comprising salt; and/or a solution of a phosphorus-comprisingsalt. The solutions used in the modified precipitate forming step can bemade in any suitable solvent. In one aspect, aqueous solutions can beused. In a specific aspect, the solvent can be is water (H₂O).

In the precipitate separation step (d) as described herein, the modifiedprecipitate (i.e. the solid phase of the mixture that is formed aftercompleting the modified precipitate forming step (c)) is separated fromthe liquid (i.e. the liquid phase of the mixture that is formed aftercompleting the modified precipitate forming step (c)) using anyconventional method which allows the separation of a precipitate from asolvent. Suitable methods include, but are not limited to, filtering,decanting and centrifugation. Subsequently the obtained precipitate iswashed using the solvent in which the solutions were made, for example,with water or distilled water. The modified precipitate is then dried,for example, at about 110-120° C. for about 4-16 hours to form a driedprecipitate.

In the calcining step (e) as described herein, the dried precipitate iscalcined in air to form a calcined catalyst precursor. In one aspect,the dried precipitate is calcined at about 500-600° C. for about 4-24hours. The calcined but unreduced catalyst mainly comprises the spinelCo₂MnO₄.

After calcination, the calcined catalyst precursor can be formed intopellets using any conventional method. Said pellets can subsequently besieved to obtain regularly sized particles. Said particles can be sizedbetween about 0.65-0.85 mm.

In the reducing step (f) as described herein, the calcined catalystprecursor is contacted with a reducing agent. This is to partiallyreduce the comprised Co to its metallic state and results in theformation of cobalt manganese oxide comprising catalyst as definedherein. In addition thereto, the catalyst composition comprises metallicCo supported on MnO at the end of the reducing step. Hence, the MnO isnot reduced completely into metallic Mn. Accordingly, the catalystcomposition of the present invention, inter alia comprising metalliccobalt, MnO and mixed spinels having the formula Co₂MnO₄ and Co₂Mn₂O₂,is obtainable by the herein described method for preparing a catalystcomposition after the “reducing step” is finished. Suitable reducingagents include, but are not limited to, CO and H₂.

Accordingly, the reducing step is very important for the method forpreparing a catalyst composition of the present invention. When thereducing step is performed too mild, an insufficient amount of Co isreduced to its metallic state. When the reducing step is performed tooharsh, the catalyst composition comprises an insufficient amount of“cobalt manganese oxide” and/or MnO. The skilled person can easilydetermine that the catalyst obtained catalyst composition comprisesmetallic cobalt, MnO and cobalt manganese oxide by using standardanalytical techniques, including X-ray diffraction.

Any suitable reducing agent can be used in the reducing step of thisinvention. In one aspect, the reducing step is performed using areducing agent in the gas phase. In one aspect, the reducing agent canbe selected from the group consisting of hydrogen (H₂) and carbonmonoxide (CO). The reduction can be carried out at ambient temperatureor at elevated temperature. In one aspect, the reduction is carried outat a temperature of at least about 300° C.; at least about 350° C. andup to about 500° C.; or up to about 450° C. In one aspect, calcinedcatalyst precursor is contacted with a reducing agent for at least about14 hrs; at least about 16 hrs and up to about 24 hrs; or up to about 20hrs.

In another aspect, the reducing step is performed “in situ”. The term“in situ” is well known in the field of chemical engineering and refersto industrial plant operations or procedures that are performed inplace. For example, aged catalysts in industrial reactors can beregenerated in place (in situ) without being removed from the reactors;see e.g. WO 03/041860 and WO 03/076074. In the context of the presentinvention, accordingly, a catalyst composition that is reduced in siturefers to a catalyst composition wherein the reducing step is performedin place, i.e. in the same enclosure that is later present in theprocess installation in which the catalysed process takes place. In oneembodiment, the reducing step as defined herein is performed while the“calcined catalyst precursor” is already present in the catalystenclosure that is situated in the process installation wherein thecatalyst composition is to be employed. In a further embodiment, thereducing step as defined herein is performed while the “calcinedcatalyst precursor” is already present in the catalyst enclosure whichcan be directly placed into said process installation.

In a further embodiment of the present invention a catalyst compositionobtainable by the herein above described method for preparing a catalystcomposition is provided. Accordingly, the present invention relates to acatalyst composition obtainable by the method comprising the steps:

-   (a) preparing a solution of cobalt- and manganese-comprising salts    to form a cobalt-manganese-solution;-   (b) admixing to the cobalt-manganese-solution to form a precipitate    by addition of alkaline solution;-   (c) admixing a hydrophilic silica and a solution of a at least one    lanthanum, phosphorus, Fe, Zr and Zn sal, such as a solution of a    lanthanum-comprising salt; and/or a solution of a    phosphorus-comprising salt, such as, for example, a solution of a    salt comprising one or more elements selected from the group    consisting of alkali metal elements, alkaline earth metal elements    and transition metal elements so as to form a solid that can be    evaporated and dried, and then added to the solution comprising the    precipitate of Co and Mn formed in step (b) to form a modified    precipitate;-   (d) separating the modified precipitate from the liquid, washing and    drying the modified precipitate to form a dried precipitate;-   (e) calcining the dried precipitate in air to form a calcined    catalyst precursor; and-   (f) contacting the calcined catalyst precursor with a reducing and    passivation agent.

In a further embodiment, the present invention relates to a process forproducing a product stream comprising a mixture of aliphatic andaromatic hydrocarbons comprising contacting the catalyst composition asdescribed herein with a gaseous mixture comprising hydrogen and carbonmonoxide (syngas mixture). In one aspect, the product stream comprisinga mixture of aliphatic and aromatic hydrocarbons can be produced byFischer-Tropsch synthesis.

The terms “aliphatic hydrocarbons” and “aromatic hydrocarbons” are verywell known in the art. Accordingly, an “aliphatic hydrocarbons” relatesto acyclic or cyclic, saturated or unsaturated hydrocarbon compoundsthat are not aromatic hydrocarbons. The term “aromatic hydrocarbons”relates to cyclically conjugated hydrocarbons with a stability (due todelocalization) that is significantly greater than that of ahypothetical localized structure (e.g. Kekulé structure). The mostcommon method for determining aromaticity of a given hydrocarbon is theobservation of diatropicity in the ¹H NMR spectrum.

In the context of the present invention, it was surprisingly found thatsubstantially no waxes are produced in the process for Fischer-Tropschsynthesis of the present invention. Moreover, it was found that theselectivity for lower hydrocarbons having between 2 and 5 carbon atoms(C2-C5 HC) and aromatic hydrocarbons is increased.

In the process of the present invention, the catalyst composition canbe, in one aspect, comprised in a fixed bed reactor or a fluidized bedreactor.

In another aspect, the syngas mixture has a hydrogen (H₂) to carbonmonoxide (CO) molar ratio of about 1-4 (i.e. H₂: CO is 1: about 1-4).The term “syngas mixture” as used herein relates to a gaseous mixturecomprising substantially hydrogen (H₂) and carbon monoxide (CO). Thesyngas mixture, which is used as a feed stream to the present processfor producing aliphatic and aromatic hydrocarbons, can comprise up to 10mol-% of other components such as CO₂ and lower hydrocarbons (lower HC).Said other components can be side-products or unconverted productsobtained in the process used for producing the syngas mixture. Inanother aspect, the syngas mixture comprises substantially no molecularoxygen (O₂). As used herein, the term “syngas mixture comprisingsubstantially no O₂” relates to a syngas mixture which comprises such alow amount of O₂ so that the comprised O₂ does not interfere with theFischer-Tropsch synthesis reaction. In another aspect, the syngasmixture comprises not more than 1 mol-% O₂; not more than 0.5 mol-% O₂;or not more than 0.4 mol-% O₂.

The process conditions useful in the process of the present inventioncan be easily determined by the person skilled in the art; see Dry(2004) Stud. Surf. Sci. Catal 152:197-230 in “Fischer-Tropschtechnology” eds. Steynberg and Dry. Accordingly, the Fischer-Tropschsynthesis is performed at a reaction temperature of about 150-350° C., aspace velocity of about 400-5000 h⁻¹, for example, about 2000 h⁻¹ and apressure of between atmospheric and about 5 MPa. The catalyst can bestabilized for about 80-100 hours at about 150-350° C. before actualuse.

In this respect, it should be noted that the reaction conditions have amarked effect on the catalytic performance. It has been reported thatselectivity on a carbon basis is essentially a function of theprobability of chain growth, α; see Dry (2004) loc. cit. Control of theproduct selectivity is to a large extent determined by the factors thatinfluence the value of α. The main factors are the temperature of thereaction, the gas composition and more specifically the partialpressures of the various gases in contact with catalyst inside thereactor. Overall, by manipulating these factors a high degree offlexibility can be obtained regarding the type of product and the carbonrange. An increase in FT-synthesis operating temperature shifts theselectivity profile to lower carbon number products. Desorption ofgrowing surface species is one of the main chain termination steps andsince desorption is an endothermic process so a higher temperatureshould increase the rate of desorption which will result in a shift tolower molecular mass products. Similarly, the higher the CO partialpressure the more is the catalyst surface covered by adsorbed monomers.The lower the coverage by partially hydrogenated CO monomers the higherthe probability of chain growth is expected to be; see also Mirzaei etal., Adv. Phys. Chem., 2009, 1-12. Accordingly, the two key stepsleading to chain termination are desorption of the chains yieldingalkenes and hydrogenation of the chains to yield alkanes.

In a further embodiment, the present invention relates to a process forproducing a product stream comprising a mixture of aliphatic andaromatic hydrocarbons comprising the method for preparing the catalystcomposition as described herein and contacting the obtained catalystcomposition with a syngas mixture.

In the present invention, the product stream comprising a mixture ofaliphatic and aromatic hydrocarbons can, in one aspect, be produced byFischer-Tropsch synthesis.

Accordingly, the present invention provides a process for producing aproduct stream comprising a mixture of aliphatic and aromatichydrocarbons, for example, by Fischer-Tropsch synthesis, comprising:

-   (a) preparing a solution of cobalt- and manganese-comprising salts    to form a heated cobalt-manganese-solution;-   (b) admixing ammonium hydroxide or sodium carbonate solution to the    cobalt-manganese-solution to form a precipitate;-   (c) admixing a hydrophilic silica and a solution of a at least one    lanthanum, phosphorus, Fe, Zr and Zn sal, such as a solution of a    lanthanum-comprising salt; and/or a solution of a    phosphorus-comprising salt; such as, for example, a solution of a    salt comprising one or more elements selected from the group    consisting of alkali metal elements, alkaline earth metal elements    and transition metal elements to the solution comprising the    precipitate of Co and Mn formed in step (b) to form a modified    precipitate;-   (d) separating the modified precipitate from the liquid, washing and    drying the modified precipitate to form a dried precipitate;-   (e) calcining the dried precipitate in air to form a calcined    catalyst precursor;-   (f) contacting the calcined catalyst precursor with a reducing agent    to produce a catalyst composition; and-   (g) contacting the obtained catalyst composition with a syngas    mixture.

In other aspects, the present invention provides methods for utilizingthe catalyst systems described herein for the production of desirableF-T hydrocarbon products. In the various embodiments described below,with respect to F-T processes, the first catalyst composition cancomprise the promoting elements dispersed hydrophilic silica containingthe catalyst composition described above.

Integrated Process

In the process according to the present invention, the syngas is firstcontacted with a first catalyst composition to be converted to a firstproduct stream, for example, by Fischer-Tropsch synthesis. The firstproduct stream comprises ethylene, propylene and aliphatic hydrocarbonshaving 4 or more carbon atoms. The first product stream can furthercomprise other components such as methane, ethane, propane, aromatichydrocarbons and CO₂.

In one aspect, the aliphatic hydrocarbons having 4 or more carbon atomscomprises aliphatic hydrocarbons having 4-10 carbon atoms; 4-8 carbonatoms; or 4-6 carbon atoms.

In one aspect, the aliphatic hydrocarbons having 4 or more carbon atomsessentially consist of aliphatic hydrocarbons having 4-10 carbon atoms;4-8 carbon atoms; or 4-6 carbon atoms. The term “essentially consist of”in this context can mean at least 95 wt %, at least 99 wt % or at least99.5 wt %.

The aliphatic hydrocarbons having 4 or more carbon atoms can comprisee.g. butane, butene, pentane, pentene, hexane and hexene. The aliphatichydrocarbons having 4 or more carbon atoms can, in one aspect, comprise1-butene and 1-hexene.

The first product stream is split into two product streams: a productstream of aliphatic hydrocarbons having 4 or more carbon atoms and aproduct stream of aliphatic hydrocarbons having 3 or less carbon atoms.This step can be done by a depropanizer, which is well-known to theskilled person.

The first product stream is split into a second product streamcomprising at least 90 wt % of said aliphatic hydrocarbons having 4 ormore carbon atoms and a third product stream comprising ethylene andpropylene. The second product stream can, in one aspect, comprise atleast 95 wt %, at least 99 wt %; or at least 99.5 wt % of said aliphatichydrocarbons having 4 or more carbon atoms. The remainder of the secondproduct stream is the component of the first product stream. In anotheraspect, the third product stream comprises aliphatic hydrocarbons having4 or more carbon atoms.

The third product stream comprises no or little amount of aliphatichydrocarbons having 4 or more carbon atoms. The third product streamcan, in one aspect, comprise at most 10 wt %; at most 5 wt %; or at most1 wt % or more, for example at most 0.5 wt % of the aliphatichydrocarbons having 4 or more carbon atoms. In another aspect, the thirdproduct stream does not comprise the aliphatic hydrocarbons having 4 ormore carbon atoms.

The third product stream comprises ethylene and propylene. In the caseswhere the third product stream comprises other components, said othercomponents can, in one aspect, be other aliphatic hydrocarbons having 3or less carbon atoms such as methane, ethane and propane. In anotheraspect, the third product stream comprises at least 90 wt %; at least 95wt %; at least 99 wt %; or at least 99.5 wt % of aliphatic hydrocarbonshaving 3 or less carbon atoms.

In another aspect, a large portion of the third product stream isethylene and propylene. In other aspects, the third product streamcomprises at least 30 wt %; at least 50 wt %; at least 75 wt %; or atleast 90 wt % of ethylene and propylene.

Ethylene and propylene are separated from the third product stream so asto form a first ethylene stream and a first propylene stream.

Further, the second product stream is converted into a fourth productstream comprising ethylene and/or propylene. The fourth product streamcan be split into a second ethylene stream and a second propylenestream. The first and second ethylene and/or the first and secondpropylene stream can be combined.

The process according to the present invention has an advantage thatethylene and propylene are obtained in two ways. Ethylene and propyleneare directly obtained from the syngas by a conversion using the firstcatalyst composition. Furthermore, the aliphatic hydrocarbons having 4or more carbon atoms from the first product stream is converted toethylene and/or propylene. Hence, the process according to the presentinvention results in an overall high yield of ethylene and/or propylene.

In one aspect, the fourth product stream comprising ethylene and/orpropylene is mixed with the first product stream. This can be done byfeeding said fourth product stream back to the unit for splitting thefirst product stream into the second and the third product streams, e.g.depropanizer. During the conversion of the second product stream,aromatics can also be produced, mainly benzene, toluene and xylene.Before the fourth product stream is mixed with the first product stream,these aromatics can, in one aspect, be separated from the fourth productstream.

The first product stream can further comprise methane, ethane andpropane. In this case, methane, ethane and propane in the first productstream can be included in the third product stream by the splitting stepof the first product stream. In this case, step c) can comprise thesteps of:

-   c1) removing methane from the third product stream to obtain a fifth    product stream comprising ethane, ethylene, propane and propylene,-   c2) separating the fifth product stream into a sixth product stream    comprising ethane and ethylene and a seventh product stream    comprising propane and propylene,-   c3) removing ethane from the sixth product stream to form the first    ethylene stream and-   c3′) removing propane from the seventh product stream to form the    first propylene stream,

In step c1), methane is removed from the third product stream. Theremaining product stream, i.e. the fifth product stream comprisesethane, ethylene, propane and propylene and, in one aspect, compriseslow amount of methane. The fifth product stream can comprise at most 10wt %, at most 5 wt %, at most 1 wt % or at most 0.5 wt % of methane. Thefifth product stream can comprise at least 90 wt %, at least 95 wt %, atleast 99 wt %, or at least 99.5 wt % of ethane, ethylene, propane andpropylene. This step can be done by a demethanizer, which is well-knownto the skilled person.

Subsequently, the fifth product stream is separated into a six productstream comprising ethane and ethylene and a fifth product streamcomprising propane and propylene in step c2). This can be done by adeethanizer, which is well-known to the skilled person. The sixthproduct stream can comprise at least 90 wt %, at least 95 wt %, at least99 wt %, at least 99.5 wt % of ethane and ethylene. The seventh productstream can comprise at least 90 wt %, at least 95 wt %, at least 99 wt%, or at least 99.5 wt % of propane and propylene.

Subsequently, the sixth product stream is separated into ethane andethylene e.g. by a C2 splitter and the seventh product stream isseparated into propane and propylene e.g. by a C3 splitter.

In one aspect, propane removed from the seventh product stream in stepc3′) is dehydrogenated into propylene and mixed with the seventh productstream. The propylene obtained can be fed back to the C3 splitter. Thisresults in an even higher overall yield of propylene. Suitable ways fordehydrogenation of propane into propylene is well-known to the skilledperson.

In another aspect, methane removed from the third product stream of stepc1) is added to the syngas. This stream comprising methane can becollected from the demethanizer into a recycle unit and fed from therecycle unit to the syngas generation unit for feeding the syngas.Similarly, in one aspect, ethane removed from the sixth product streamin step c3) can be added to the syngas. Ethane can be collected from theC2 splitter into a recycle unit and fed from the recycle unit to thesyngas generation unit for feeding the syngas. The recycle unit forcollecting methane and ethane can be the same unit and can mix methaneand ethane before feeding the mixture gas to the syngas generation unit.

The terms “aliphatic hydrocarbons” and “aromatic hydrocarbons” are verywell known in the art. Accordingly, an “aliphatic hydrocarbons” relatesto acyclic or cyclic, saturated or unsaturated hydrocarbon compoundsthat are not aromatic hydrocarbons. The term “aromatic hydrocarbons”relates to cyclically conjugated hydrocarbons with a stability (due todelocalization) that is significantly greater than that of ahypothetical localized structure (e.g. Kekuléstructure). The most commonmethod for determining aromaticity of a given hydrocarbon is theobservation of diatropicity in the ¹H NMR spectrum.

In the context of the present invention, it was surprisingly found thatsubstantially no waxes are produced in the process for Fischer-Tropschsynthesis of the present invention. Moreover, it was found that theselectivity for lower hydrocarbons having between 2 and 5 carbon atoms(C2-C5 HC) and aromatic hydrocarbons is increased.

In the process of the present invention, the first catalyst compositioncan, in one aspect, be in a fixed bed reactor or a fluidized bedreactor.

In a further embodiment, the present invention relates to the processfor producing ethylene and propylene as described above comprising themethod for preparing the first catalyst composition as described herein.

In one aspect of the present invention, the first product stream can beproduced by Fischer-Tropsch synthesis.

Second Catalyst Composition

According to the process of the present invention, the second productstream is converted into a fourth product stream comprising ethyleneand/or propylene. In one aspect, this can be performed by contacting thesecond product stream with a second catalyst composition suitable forconverting aliphatic hydrocarbons having 4 or more carbon atoms intoethylene and/or propylene. In one aspect, the second catalystcomposition is an olefin metathesis catalyst or C₄ to C₈ crackingcatalyst suitable for converting 1-butylene and 1-hexene into ethyleneand propylene.

Suitable examples for the second catalyst composition include an olefinmetathesis catalyst. Examples of suitable catalysts are described e.g.in U.S. Pat. No. 6,586,649, which is incorporated herein by reference interms of the catalyst:

The second catalyst composition can be at least one metal oxide selectedfrom the group consisting of the oxides of the transition metals.

In one aspect, the transition metal oxide catalyst in the secondcatalyst composition can be selected from oxides of molybdenum, or ofrhenium or of tungsten, or of mixtures of any two or more of tungsten,rhenium and molybdenum. This catalyst can be a homogeneous (unsupported)catalyst or a heterogeneous (supported) catalyst. In another aspect, thecatalyst can be supported and any convenient support can be used,provided it neither interferes with nor inhibits the metathesis step ofthe process according to the invention. Suitable supports include thosebased on or including ceramic supports such as silica, alumina, titania,zirconia or mixtures thereof. In a specific aspect, a suitable supportcan be silica. The catalyst can be attached to its support in anyconvenient fashion, such as those known in the art, in particular bysublimation or by wet impregnation. The transition metal oxideconstituent of the catalyst can amounts to 1-30% by mass of the totalcatalyst mass (transition metal and support together), for example,6-20% thereof. In particular the catalyst can be a WO₃-based (tungstenoxide-based) catalyst containing Cs (caesium) as a promoter.

In the cases where the second catalyst composition is a supportedcatalyst type, the transition metal oxide can form e.g. 1-30% by mass ofthe total heterogeneous catalyst mass. In particular, the catalyst ofthe heterogeneous catalyst mass can comprise tungsten oxide, beingsupported on silica, the catalyst mass containing a promoter selectedfrom the group consisting of cesium (to decrease selectivity towardspropylene) and phosphates (to increase selectivity towards propylene).

In one aspect, the second catalyst composition has as high a proportionof acid sites thereon as practicable. Acidity of the catalyst can beenhanced by treating the catalyst with organic acids or inorganic acids,or by impregnation thereof with cations such as those of phosphates orborates. Acidity of the catalyst can, conversely, be reduced by blockingacid sites thereon, by means of alkaline earth metals.

Many other suitable olefin metathesis catalysts are known, for exampleas described in U.S. Pat. Nos. 8,153,851 and 5,990,369.

The present invention will now be more fully described by the followingnon-limiting Examples and figures.

In FIG. 1, feedstock 1 such as natural gas, coal, biomass or municipalsolid waste is fed to the syngas generation unit. The syngas generated 2is contacted with a first catalyst composition (catalyst A) to obtain afirst product stream 3 comprising ethylene and propylene and aliphatichydrocarbons having 4 or more carbon atoms. The first product stream 3is fed to a C4+ separator to split the first product stream 3 into asecond product stream 5 comprising at least 90 wt % of said aliphatichydrocarbons having 4 or more carbon atoms and a third product stream 4comprising ethylene and propylene.

The third product stream 4 is fed to a C2/C3 separator to separateethylene and propylene in the third product stream 4. A first ethylenestream 17 and a first propylene stream 16 are obtained.

The second product stream 5 is contacted with a second catalystcomposition (catalyst B) so that a fourth product stream 8 comprisingethylene and/or propylene is produced.

FIG. 2 shows a further embodiment of the process according to thepresent invention. Feedstock 1 is fed to the syngas generation unitwhich produces syngas 2. The syngas 2 is contacted with the firstcatalyst composition (catalyst A) to obtain a first product stream 3.The first product stream 3 is fed to the depropanizer to split the firstproduct stream 3 into a second product stream 5 comprising at least 90wt % of the aliphatic hydrocarbons having 4 or more carbon atoms and athird product stream 4 comprising ethylene and propylene.

The second product stream 5 is contacted with a second catalystcomposition in the olefin conversion unit, which produces a fourthproduct stream 8 comprising ethylene and propylene and a product stream11 comprising BTX. The fourth product stream 8 is fed back to thedepropanizer and is mixed with the first product stream 3.

The third product stream 4 is fed to the demethanizer and methane 6 isremoved from the third product stream 4, producing a fifth productstream 7 which comprises ethane, ethylene, propane and propylene.Methane 6 is fed to the recycle unit, which removes undesired components12 and feeds the remainder 18 to the syngas generation unit.

The fifth product stream 7 is fed to the deethanizer and is separatedinto a sixth product stream 10 comprising ethane and ethylene and aseventh product stream 9 comprising propane and propylene.

The sixth product stream 10 is fed to the C2 splitter, which separatesethane 13 and ethylene 17. Ethane 13 is fed to the recycle unit, whichremoves undesired compounds 12 and feeds the remainder 18 to the syngasgeneration unit.

The seventh product stream 9 is fed to the C3 splitter, which separatespropane 15 and propylene 16. Propane 15 is fed to the propanedehydrogenation unit, which dehydrogenates propane into propylene 14.Propylene 14 is fed back to the C3 splitter.

EXAMPLE 1 (Comparative)

CoMnLaP (Comprising 0.1 wt-% La and 0.03 wt-% P)

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80° C.in a round bottom flask. Ammonium hydroxide solution (5.6 M/I) preheatedat 80° C. was added to the nitrate solution, which was continuouslystirred whilst the temperature was maintained at 80° C. The pH wasvaried from 2.80 to 8.0. The desired quantity of lanthanum nitrate(0.0117 g) was dissolved in 3.4 ml of distilled water and was addedslowly into the of CoMn catalyst precipitate (5 g) followed by additionof 0.0064 g of ammonium phosphate dissolved in 3.4 ml of distilledwater. The resulting precipitate was mixed thoroughly to make ahomogeneous mixture. Material was dried at 110° C. for 16 h-24 h andcalcined at 500-600° C. for 24 h. The calcined catalyst precursor waspelleted and sieved to obtain 0.65-0.85 mm sized particles. Calcinedprecursor particles (0.5 g) were loaded into a fixed-bed reactor andtested at standard conditions.

EXAMPLE 2

CoMnP (Comprising 0.05 wt-% P)

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80° C.in a round bottom flask. Ammonium hydroxide solution (5.6 M/I) preheatedat 80° C. was added to the nitrate solution, which was continuouslystirred whilst the temperature was maintained at 800° C. The pH wasvaried from 2.80 to 8.0. the desired quantity of ammonium phosphate(0.0107 g) dissolved in 3.4 ml of distilled water was added slowly intothe of CoMn catalyst precipitate (5 g). The resulting precipitate wasmixed thoroughly to make a homogeneous mixture. Material was dried at110° C. for 16 h-24 h and calcined at 500-600° C. for 24 h. The calcinedcatalyst precursor was pelleted and sieved to obtain 0.65-0.85 mm sizedparticles. Calcined precursor particles (0.5 g) were loaded into afixed-bed reactor and tested at standard.

EXAMPLE 3

CoMnSiLaP

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80-90°C. in a round bottom flask. 1.2 g of hydrophilic silica having a pH ofrfrom about 3.7 to about 4.7 and a specific surface area of 200 m²/g to400 m²/g, 0.005 g of lanthanum nitrate, and 0.005 g of ammoniumphosphate were dissolved in 20-50 ml of water under continues agitationfor 1-2 hrs at temperature where water does not evaporate. The resultingmixture was dried by the incipient wetness method. Resultant solid wasadded to Co/Mn solution. Sodium carbonate 1 M solution preheated at 60to 80° C. was added to this Co/Mn solution, which was continuouslystirred whilst the temperature was maintained at 80° C. The pH wasvaried from 2.80 to 9 by addition of carbonate solution. Resultingprecipitate were aged for ½ to 8 hr followed by separating ofprecipitate from the liquid. The resulting precipitate were washed tillsodium free. Material was dried at 110-120° C. for 16 h-24 h and cookedat 300-500° C. for 4-24 h followed by passivation of catalyst precursorwith an appropriate media and thermal treatment. The catalyst precursorwas pelleted and sieved to obtain 40-60 mesh sized particles. Catalystparticles (0.5 g) were loaded into a fixed-bed reactor and tested atstandard conditions.

EXAMPLE 4

CoMnSiLaP

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80-90°C. in a round bottom flask. 1.2 g of hydrophilic silica having a pH offrom about 3.7 to about 4.7 and a specific surface area of 200 m²/g to400 m²/g; 0.01 g of lanthanum nitrate, and 0.01 g of ammonium phosphatewere dissolved in 20-50 ml of water under continues agitation for 1-2hrs at temperature where water does not evaporate. The resulting mixturewas dried by the incipient wetness method. Resultant solid was added toCo/Mn solution. Sodium carbonate 1 M solution preheated at 60 to 80° C.was added to this Co/Mn solution, which was continuously stirred whilstthe temperature was maintained at 80° C. The pH was varied from 2.80 to9 by addition of carbonate solution. Resulting precipitate were aged for½ to 8 hr followed by separating of precipitate from the liquid. Theresulting precipitate were washed till sodium free. Material was driedat 110-120° C. for 16 h-24 h and cooked at 300-500° C. for 4-24 hfollowed by passivation of catalyst precursor with an appropriate mediaand thermal treatment. The catalyst precursor was pelleted and sieved toobtain 40-60 mesh sized particles. Catalyst particles (0.5 g) wereloaded into a fixed-bed reactor and tested at standard conditions.

EXAMPLE 5

CoMnSiLaP

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80-90°C. in a round bottom flask. 1.2 g of hydrophilic silica having a pH offrom about 3.7 to about 4.7 and a specific surface area of 200 m²/g to400 m²/g, 0.031 g of lanthanum nitrate and 0.01 g of ammonium phosphatewere dissolved in 20-50 ml of water under continues agitation for 1-2hrs at temperature where water does not evaporate. The resulting mixturewas dried by the incipient wetness method. Resultant solid was added toCo/Mn solution. Sodium carbonate 1 M solution preheated at 60 to 80° C.was added to this Co/Mn solution, which was continuously stirred whilstthe temperature was maintained at 80° C. The pH was varied from 2.80 to9 by addition of carbonate solution. Resulting precipitate were aged for½ to 8 hr followed by separating of precipitate from the liquid. Theresulting precipitate were washed till sodium free. Material was driedat 110-120° C. for 16 h-24 h and cooked at 300-500° C. for 4-24 hfollowed by passivation of catalyst precursor with an appropriate mediaand thermal treatment. The catalyst precursor was pelleted and sieved toobtain 40-60 mesh sized particles. Catalyst particles (0.5 g) wereloaded into a fixed-bed reactor and tested at standard conditions.

EXAMPLE 6

CoMnZnSi

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80-90°C. in a round bottom flask. 1.2 g of hydrophilic silica having a pH offrom about 3.7 to about 4.7 and a specific surface area of 200 m²/g to400 m²/g, and 2.98 g of Zinc nitrate were dissolved in 20-50 ml of waterunder continues agitation for 1-2 hrs at temperature where water doesnot evaporate. The resulting mixture was dried by the incipient wetnessmethod. Resultant solid was added to Co/Mn solution. Sodium carbonate 1M solution preheated at 60 to 80° C. was added to this Co/Mn solution,which was continuously stirred whilst the temperature was maintained at80° C. The pH was varied from 2.80 to 9 by addition of carbonatesolution. Resulting precipitate were aged for ½ to 8 hr followed byseparating of precipitate from the liquid. The resulting precipitatewere washed till sodium free. Material was dried at 110-120° C. for 16h-24 h and cooked at 300-500° C. for 4-24 h followed by passivation ofcatalyst precursor with an appropriate media and thermal treatment. Thecatalyst precursor was pelleted and sieved to obtain 40-60 mesh sizedparticles. Catalyst particles (0.5 g) were loaded into a fixed-bedreactor and tested at standard conditions.

EXAMPLE 7

CoMnFeSi

100 ml of Co and Mn (1 M solutions) were premixed and heated to 80-90°C. in a round bottom flask. 1.2 g of hydrophilic silica having a pH offrom about 3.7 to about 4.7 and a specific surface area of 200 m²/g to400 m²/g, and 3.62 g of iron nitrate were dissolved in 20-50 ml of waterunder continues agitation for 1-2 hrs at temperature where water doesnot evaporate. The resulting mixture was dried by the incipient wetnessmethod. Resultant solid was added to Co/Mn solution. Sodium carbonate 1M solution preheated at 60 to 80° C. was added to this Co/Mn solution,which was continuously stirred whilst the temperature was maintained at80° C. The pH was varied from 2.80 to 9 by addition of carbonatesolution. Resulting precipitate were aged for ½ to 8 hr followed byseparating of precipitate from the liquid. The resulting precipitatewere washed till sodium free. Material was dried at 110-120° C. for 16h-24 h and cooked at 300-500° C. for 4-24 h followed by passivation ofcatalyst precursor with an appropriate media and thermal treatment. Thecatalyst precursor was pelleted and sieved to obtain 40-60 mesh sizedparticles. Catalyst particles (0.5 g) were loaded into a fixed-bedreactor and tested at standard conditions.

TABLE 1 CATALYST ACTIVITY EXAMPLE 1 2 3 4 5 6 7 Catalyst CoMnLaP CoMnPCoMnSiLaP CoMnSiLaP CoMnSiLaP CoMnSiZn CoMnSiFe Conversion % 42.4 21.783.8 58.5 60.2 76 81 Methane 13.1 14.2 4.7 11.7 13 29.5 31.5 Paraffin25.2 21.4 18.3 19.7 20.5 20 21.5 Total 55.4 56.4 67.5 60.3 56 20.4 33.5Olefins CO₂ 6.3 8 14.2 8.3 10.5 30.1 13.5

Table 1 shows that the catalyst of the present invention has asignificantly increased activity when compared to a catalyst without theSi_(b) component. Table 1 show that the catalyst of the presentinvention, which includes the Si_(b) component has a significantlyincreased activity when compared to a other and conventional cobaltmanganese oxide F-T catalyst. For example, the catalysts in Examples, 3,4, and 5 shows increased conversion rates and increased production inolefins. In addition thereto, the catalysts form Examples 3, 4, and 5,shows a decrease methane formation, which is an undesired side-productproduced in F-T synthesis.

EXAMPLE 8

Ethylene and propylene were produced from syngas according to the schemeas illustrated in FIG. 2.

A catalyst composition as described herein can be used as the firstcatalyst composition (catalyst A), i.e. the first catalyst compositionused is unsupported and comprises cobalt; manganese; and at least oneelement selected from the group of lanthanum and phosphorus, wherein therelative molar ratios of the elements comprised in said composition arerepresented by the formulaCoMn_(a)La_(b)P_(c)M_(d)O_(x)wherein:

-   -   M is one or more elements selected from the group consisting of        alkali metal, alkaline earth metal and transition metal;    -   a is about 0.8-1.2;    -   b and/or c is from greater than 0 to about 0.005;    -   d is from 0 to about 0.005; and    -   x is a number determined by the valence of the other elements        present.

It should be noted that the first catalyst composition can also comprisea hydrophilic silica containing catalyst, as described herein. Theobtained first product stream had a composition as shown in Table 2.

The aliphatic hydrocarbons having 4 or more carbon atoms (indicated asC4+) was fed to an olefin conversion unit. The obtained product streamcontained a major amount of ethylene and propylene and a minor amount ofBTX, as can be seen in Table 1.

Hence, the total amount of the obtained ethylene and propylenesignificantly increased by the conversion of C4+ into ethylene andpropylene compared to the case in which only the first catalystcomposition was used.

TABLE 2 First Feed to Products Syngas product olefin of olefin Feedstream conversion unit conversion unit Total % Kg/hr Kg/hr Kg/hr Kg/hrKg > hr Increase Ar CO 206938 16063 H2 41870 23892 N2 560 560 CO2 5149C2 2571 C2═ 16994 12024 29018 C3 2231 C3═ 25492 18041 43533 C4+ 3757037570 BTX 340 total 130522 37570 30065 Total C2 42486 72551 70.8 C3olefins

EXAMPLE 9

In this example, propane obtained by C3 splitter was fed to a propanedehydrogenation unit. This resulted in an even higher amount ofpropylene in the final product, as shown in Table 3.

TABLE 3 First Feed To Products Syngas product olefin of olefin Feedstream conversion unit conversion unit Feed to PDH Total % Kg/hr Kg/hrKg/hr Kg/hr PDH Product Kg/hr Increase Ar CO 206938 16063 H2 41870 23892N2 560 560 CO2 5149 C2 2571 C2═ 16994 12024 29018 C3 2231 2231 C3═ 2549218041 2130 45663 C4+ 37570 37570 BTX 340 total 130522 37570 30065 TotalC2 42486 74681 75.8 C3 olefins

The invention claimed is:
 1. A catalyst composition comprising cobalt;manganese; hydrophilic silica; and at least one element selected fromthe group consisting of lanthanum, phosphorus, Fe, Zr, and Zn, whereinthe relative molar ratios of the elements comprised in the compositionare represented by the formulaCoMn_(a)Si_(b)XcM_(d)O_(y) wherein: M is one or more elements selectedfrom the group consisting of alkali metal, alkaline earth metal, andtransition metal; a is about 0.8-1.2; b is 0.1 to 1; each c is fromgreater than 0 to about 0.005, wherein the total c is from greater than0 to about 0.005; d is 0 to about 0.005; X is at least one elementselected from the group consisting of lanthanum, phosphorus, Fe, Zr, andZn; y is a number determined by the valence of the other elementspresent; and Si_(b) is present as part of the catalyst composition. 2.The catalyst according to claim 1, wherein M is selected from the groupconsisting of sodium (Na), potassium (K), rubidium (Rb), caesium (Cs),magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), titanium(Ti), and zirconium (Zr).
 3. The catalyst composition according to claim1, wherein X is two elements, wherein the elements are lanthanum andphosphorus, and wherein c for each of lanthanum and phosphorus is fromgreater than 0 to about 0.005.
 4. The catalyst composition according toclaim 1, wherein the hydrophilic silica has a pH of 3.7-4.7.
 5. Thecatalyst composition according to claim 1, wherein the hydrophilicsilica has a specific surface area of 200 m²/g to 400 m²/g.
 6. Thecatalyst composition according to claim 1, wherein X is one element andwherein the element is selected from the group consisting of Fe, Zr, andZn.
 7. The catalyst composition according to claim 1, wherein thecatalyst has at least one of lower methane formation, lower carbondioxide formation, higher activity, higher conversion of syngas, orhigher total olefins formation as compared to the same catalyst withoutthe Si_(b) component.
 8. The catalyst composition of claim 1, whereinthe hydrophilic silica comprises a pyrogenic silica.
 9. A method forpreparing the catalyst composition of claim 1, comprising the steps: (a)preparing a solution of cobalt- and manganese-comprising salts to form acobalt-manganese-solution; (b) admixing an alkaline solution to thecobalt-manganese-solution to form a precipitate; (c) admixing ahydrophilic silica and a solution of at least one of a lanthanum,phosphorus, Fe, Zr, and Zn salt; and/or a solution of aphosphorus-comprising salt; evaporating any water present therein anddrying, and then adding the resulting solid to the solution comprisingthe precipitate to form a modified precipitate; (d) separating themodified precipitate, washing and drying the modified precipitate toform a dried precipitate; (e) calcining the dried precipitate in air toform a calcined catalyst precursor; and (f) contacting the calcinedcatalyst precursor with a reducing agent.
 10. The method according toclaim 9, wherein the reducing agent is selected from the groupconsisting of hydrogen (H₂) and carbon monoxide (CO).
 11. The processaccording to claim 9, wherein the process comprises admixing a solutionof a lanthanum-comprising salt; and/or a solution of a phosphorus-comprising salt.
 12. A method of producing olefins comprising contactingsyngas with the catalyst composition of claim
 1. 13. A process forproducing a product stream comprising a mixture of aliphatic andaromatic hydrocarbons, the process comprising contacting the catalystcomposition of claim 1 with a syngas mixture.
 14. The process accordingto claim 13, wherein the product stream comprises a mixture of aliphaticand aromatic hydrocarbons produced by Fischer-Tropsch synthesis.
 15. Theprocess according to claim 13, wherein the catalyst composition is in afixed bed reactor or fluidized bed reactor.